Organic light emitting diode and organic light emitting device including the same

This application claims the benefit under 35 U.S.C. § 119(a) to Korean Patent Application No. 10-2019-0129775, filed in the Republic of Korea on Oct. 18, 2019 and No. 10-2020-0113952, filed in the Republic of Korea on Sep. 7, 2020, the entire contents of which are incorporated herein by reference into the present application.

The present disclosure relates to an organic light emitting diode, and more specifically, to an organic light emitting diode having excellent luminous properties and an organic light emitting device having the diode.

As display devices have become larger, there exists a need for a flat display device with lower spacing occupation. Among the flat display devices, a display device using an organic light emitting diode (OLED) has come into the spotlight.

In the OLED, when electrical charges are injected into an emitting material layer between an electron injection electrode (i.e., cathode) and a hole injection electrode (i.e., anode), electrical charges are recombined to form excitons, and then emit light as the recombined excitons are shifted to a stable ground state. The OLED can be formed as a thin film having a thickness less than 2000 Å and can be implement unidirectional or bidirectional images as electrode configurations. In addition, OLEDs can be formed on a flexible transparent substrate such as a plastic substrate so that OLED can implement a flexible or foldable display with ease. Moreover, the OLED can be driven at a lower voltage of 10 V or less. Besides, the OLED has relatively lower power consumption for driving compared to plasma display panels and inorganic electroluminescent devices, and the color purity of the OLED is very high. Particularly, the OLED can implement red, green and blue colors, thus it has attracted a lot of attention as a light emitting device.

Conventional fluorescent materials have shown low luminous efficiency because only the singlet excitons are involved in the luminescence process thereof. The phosphorescent materials in which triplet excitons as well as the singlet excitons are involved in the luminescence process have relatively high luminous efficiency compared to the fluorescent material. However, the metal complex as the representative phosphorescent material has too short luminous lifetime to be applicable into commercial devices.

Accordingly, embodiments of the present disclosure are directed to an OLED and an organic light emitting device including the OLED that substantially obviates one or more of the problems due to the limitations and disadvantages of the related art.

An aspect of the present disclosure is to provide an OLED that can lower its driving voltage and enhance its luminous efficiency and lifetime and an organic light emitting device including the diode.

Additional features and aspects will be set forth in the description that follows, and in part will be apparent from the description, or may be learned by practice of the inventive concepts provided herein. Other features and aspects of the inventive concepts may be realized and attained by the structure particularly pointed out in the written description, or derivable therefrom, and the claims hereof as well as the appended drawings.

To achieve these and other aspects of the inventive concept, as embodied and broadly described, an organic light emitting diode comprises: a first electrode; a second electrode facing the first electrode; and an emitting material layer disposed between the first and second electrodes, wherein the emitting material layer comprises a first compound, a second compound and a third compound, wherein the second compound comprises an organic compound having the following structure of Chemical Formula 1, and wherein the third compound comprises an organic compound having the following structure of Chemical Formula 3:

wherein each of Rand Ris independently hydrogen or an unsubstituted or substituted C-Calkyl group; and Ris an unsubstituted or substituted C-Cfused hetero aromatic group, an unsubstituted or substituted C-Caromatic amino group or an unsubstituted or substituted C-Chetero aromatic amino group;

wherein each of Rto Ris independently hydrogen, an unsubstituted or substituted C-Calkyl group, an unsubstituted or substituted C-Calkoxy group, an unsubstituted or substituted C-Caromatic group or an unsubstituted or substituted C-Chetero aromatic group, or two adjacent groups among Rto Rforms an unsubstituted or substituted C-Calicyclic ring, an unsubstituted or substituted C-Chetero alicyclic ring, an unsubstituted o substituted C-Caromatic ring or an unsubstituted or substituted C-Chetero aromatic ring; and each of Xand Xis independently a halogen atom.

In another aspect, an organic light emitting diode comprises: a first electrode; a second electrode facing the first electrode; a first emitting material layer disposed between the first and second electrodes; and a second emitting material layer disposed between the first electrode and the first emitting material layer or between the first emitting material layer and the second electrode, wherein the first emitting material layer comprises a first compound and a second compound, wherein the second emitting material layer comprises a fourth compound a fifth compound, wherein the second compound comprises an organic compound having the structure of Chemical Formula 1, and wherein the fifth compound comprises an organic compound having the structure of Chemical formula 3.

In still another aspect, an organic light emitting device comprises a substrate and the OLEDs disposed over the substrate, as described above.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the inventive concepts as claimed.

Reference and discussions will now be made below in detail to aspects, embodiments and examples of the disclosure, some examples of which are illustrated in the accompanying drawings.

The present disclosure relates to an organic light emitting diode (OLED) into which delayed fluorescent material and fluorescent material having adjusted energy levels are applied in an identical EML or adjacently disposed EMLs and an organic light emitting device having the OLED. The OLED may be applied into an organic light emitting device such as an organic light emitting display device and an organic light emitting luminescent device. As an example, a display device applying the OLED will be described.

is a schematic cross-sectional view of an organic light emitting display devicein accordance with an exemplary aspect of the present disclosure. All components of the organic light emitting device in accordance with all aspects of the present disclosure are operatively coupled and configured. As illustrated in, the organic light emitting display deviceincludes a substrate, a thin-film transistor Tr on the substrate, and an organic light emitting diode (OLED) D connected to the thin film transistor Tr.

The substratemay include, but is not limited to, glass, thin flexible material and/or polymer plastics. For example, the flexible material may be selected from the group, but is not limited to, polyimide (PI), polyethersulfone (PES), polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polycarbonate (PC) and combination thereof. The substrate, over which the thin film transistor Tr and the OLED D are arranged, form an array substrate.

A buffer layermay be disposed over the substrate, and the thin film transistor Tr is disposed over the buffer layer. The buffer layermay be omitted.

A semiconductor layeris disposed over the buffer layer. In one exemplary aspect, the semiconductor layermay include, but is not limited to, oxide semiconductor materials. In this case, a light-shield pattern may be disposed under the semiconductor layer, and the light-shield pattern can prevent light from being incident toward the semiconductor layer, and thereby, preventing the semiconductor layerfrom being deteriorated by the light. Alternatively, the semiconductor layermay include, but is not limited to, polycrystalline silicon. In this case, opposite edges of the semiconductor layermay be doped with impurities.

A gate insulating layerformed of an insulating material is disposed on the semiconductor layer. The gate insulating layermay include, but is not limited to, an inorganic insulating material such as silicon oxide (SiO) or silicon nitride (SiN).

A gate electrodemade of a conductive material such as a metal is disposed over the gate insulating layerso as to correspond to a center of the semiconductor layer. While the gate insulating layeris disposed over a whole area of the substratein, the gate insulating layermay be patterned identically as the gate electrode.

An interlayer insulating layerformed of an insulating material is disposed on the gate electrodewith covering over an entire surface of the substrate. The interlayer insulating layermay include, but is not limited to, an inorganic insulating material such as silicon oxide (SiO) or silicon nitride (SiN), or an organic insulating material such as benzocyclobutene or photo-acryl.

The interlayer insulating layerhas first and second semiconductor layer contact holesandthat expose both sides of the semiconductor layer. The first and second semiconductor layer contact holesandare disposed over opposite sides of the gate electrodewith spacing apart from the gate electrode. The first and second semiconductor layer contact holesandare formed within the gate insulating layerin. Alternatively, the first and second semiconductor layer contact holesandare formed only within the interlayer insulating layerwhen the gate insulating layeris patterned identically as the gate electrode.

A source electrodeand a drain electrode, which are formed of conductive material such as a metal, are disposed on the interlayer insulating layer. The source electrodeand the drain electrodeare spaced apart from each other with respect to the gate electrode, and contact both sides of the semiconductor layerthrough the first and second semiconductor layer contact holesand, respectively.

The semiconductor layer, the gate electrode, the source electrodeand the drain electrodeconstitute the thin film transistor Tr, which acts as a driving element. The thin film transistor Tr inhas a coplanar structure in which the gate electrode, the source electrodeand the drain electrodeare disposed over the semiconductor layer. Alternatively, the thin film transistor Tr may have an inverted staggered structure in which a gate electrode is disposed under a semiconductor layer and a source and drain electrodes are disposed over the semiconductor layer. In this case, the semiconductor layer may comprise amorphous silicon.

A gate line and a data line, which cross each other to define a pixel region, and a switching element, which is connected to the gate line and the data line, may be further formed in the pixel region of. The switching element is connected to the thin film transistor Tr, which is a driving element. Besides, a power line is spaced apart in parallel from the gate line or the data line, and the thin film transistor Tr may further include a storage capacitor configured to constantly keep a voltage of the gate electrode for one frame.

In addition, the organic light emitting display devicemay include a color filter that comprises dyes or pigments for transmitting specific wavelength light of light emitted from the OLED D. For example, the color filter can transmit light of specific wavelength such as red (R), green (G), blue (B) and/or white (W). Each of red, green, and blue color filter may be formed separately in each pixel region. In this case, the organic light emitting display devicecan implement full-color through the color filter.

For example, when the organic light emitting display deviceis a bottom-emission type, the color filter may be disposed on the interlayer insulating layerwith corresponding to the OLED D. Alternatively, when the organic light emitting display deviceis a top-emission type, the color filter may be disposed over the OLED D, that is, a second electrode.

A passivation layeris disposed on the source and drain electrodesandover the whole substrate. The passivation layerhas a flat top surface and a drain contact holethat exposes the drain electrodeof the thin film transistor Tr. While the drain contact holeis disposed on the second semiconductor layer contact hole, it may be spaced apart from the second semiconductor layer contact hole.

The OLED D includes a first electrodethat is disposed on the passivation layerand connected to the drain electrodeof the thin film transistor Tr. The OLED D further includes an emissive layerand a second electrodeeach of which is disposed sequentially on the first electrode.

The first electrodeis disposed in each pixel region. The first electrodemay be an anode and include a conductive material having a relatively high work function value. For example, the first electrodemay include, but is not limited to, a transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), tin oxide (SnO), zinc oxide (ZnO), indium cerium oxide (ICO), aluminum doped zinc oxide (AZO), and the like.

In one exemplary aspect, when the organic light emitting display deviceis a bottom-emission type, the first electrodemay have a single-layered structure of a transparent conductive material. Alternatively, when the organic light emitting display deviceis a top-emission type, a reflective electrode or a reflective layer may be disposed under the first electrode. For example, the reflective electrode or the reflective layer may include, but are not limited to, silver (Ag) or aluminum-palladium-copper (APC) alloy. In the OLED D of the top-emission type, the first electrodemay have a triple-layered structure of ITO/Ag/ITO or ITO/APC/ITO. In addition, a bank layeris disposed on the passivation layerin order to cover edges of the first electrode. The bank layerexposes a center of the first electrode.

An emissive layeris disposed on the first electrode. In one exemplary aspect, the emissive layermay have a single-layered structure of an emitting material layer (EML). Alternatively, the emissive layermay have a multiple-layered structure of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an EML, a hole blocking layer (HBL), an electron transport layer (ETL) and/or an electron injection layer (EIL) (see,). In one aspect, the emissive layermay have one emitting part. Alternatively, the emissive layermay have multiple emitting parts to form a tandem structure.

The second electrodeis disposed over the substrateabove which the emissive layeris disposed. The second electrodemay be disposed over a whole display area and may include a conductive material with a relatively low work function value compared to the first electrode. The second electrodemay be a cathode. For example, the second electrodemay include, but is not limited to, aluminum (Al), magnesium (Mg), calcium (Ca), silver (Ag), alloy thereof or combination thereof such as aluminum-magnesium alloy (Al—Mg). When the organic light emitting display deviceis a top-emission type, the second electrodeis thin so as to have light-transmissive (semi-transmissive) property.

In addition, an encapsulation filmmay be disposed over the second electrodein order to prevent outer moisture from penetrating into the OLED D. The encapsulation filmmay have, but is not limited to, a laminated structure of a first inorganic insulating film, an organic insulating filmand a second inorganic insulating film.

Moreover, the organic light emitting display devicemay have a polarizer in order to decrease external light reflection. For example, the polarizer may be a circular polarizer. When the organic light emitting display deviceis a bottom-emission type, the polarizer may be disposed under the substrate. Alternatively, when the organic light emitting display deviceis a top-emission type, the polarizer may be disposed over the encapsulation film. In addition, a cover window may be attached to the encapsulation filmor the polarizer. In this case, the substrateand the cover window may have a flexible property, thus the organic light emitting display devicemay be a flexible display device.

Now, we will describe the OLED in more detail.is a schematic cross-sectional view illustrating an OLED in accordance with an exemplary aspect of the present disclosure. As illustrated in, the OLED Dcomprises first and second electrodesandfacing each other, and an emissive layerhaving single emitting part disposed between the first and second electrodesand. The organic light emitting display deviceincludes a red pixel region, a green pixel region and a blue pixel region, and the OLED Dmay be disposed in the green pixel region. The emissive layercomprises an EMLdisposed between the first and second electrodesand. Also, the emissive layermay comprise at least one of a HTLdisposed between the first electrodeand the EMLand an ETLdisposed between the second electrodeand the EML. Also, the emissive layermay further comprise at least one of a HILdisposed between the first electrodeand the HTLand an EILdisposed between the second electrodeand the ETL. Alternatively, the emissive layermay further comprise a first exciton blocking layer, i.e. an EBLdisposed between the HTLand the EMLand/or a second exciton blocking layer, i.e. a HBLdisposed between the EMLand the ETL.

The first electrodemay be an anode that provides a hole into the EML. The first electrodemay include, but is not limited to, a conductive material having a relatively high work function value, for example, a transparent conductive oxide (TCO). In an exemplary aspect, the first electrodemay include, but is not limited to, ITO, IZO, ITZO, SnO, ZnO, ICO, AZO, and the like.

The second electrodemay be a cathode that provides an electron into the EML. The second electrodemay include, but is not limited to, a conductive material having a relatively low work function values, i.e., a highly reflective material such as Al, Mg, Ca, Ag, alloy thereof, combination thereof, and the like.

The EMLmay comprise a first compound (Compound 1, Host) H, a second compound (Compound 2, dopant 1) DF and a third compound (Compound 3, dopant 2) FD. For example, the first compound H may be a (first) host, the second compound DF may be a delayed fluorescent material DF, and the third compound FD may be a fluorescent material. The first compound H in the EMLmay comprise, but is not limited to, 9-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazole-3-carbonitrile (mCP-CN), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), 3,3′-bis(N-carbazolyl)-1,1′-biphenyl (mCBP), 1,3-Bis(carbazol-9-yl)benzene (mCP), Bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), 2,8-bis(diphenylphosphoryl)dibenzothiophene (PPT), 1,3,5-Tri[(3-pyridyl)-phen-3-yl]benzene (TmPyPB), 2,6-Di(9H-carbazol-9-yl)pyridine (PYD-2Cz), 2,8-di(9H-carbazol-9-yl)dibenzothiophene (DCzDBT), 3′,5′-Di(carbazol-9-yl)-[1,1′-bipheyl]-3,5-dicarbonitrile (DCzTPA), 4′-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile(4′-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile (pCzB-2CN), 3′-(9H-carbazol-9-yl)biphenyl-3,5-dicarbonitrile (mCzB-2CN), Diphenyl-4-triphenylsilylphenyl-phosphine oxide (TSPO1), 9-(9-phenyl-9H-carbazol-6-yl)-9H-carbazole (CCP), 4-(3-(triphenylen-2-yl)phenyl)dibenzo[b,d]thiophene, 9-(4-(9H-carbazol-9-yl)phenyl)-9H-3,9′-bicarbazole, 9-(3-(9H-carbazol-9-yl)phenyl)-9H-3,9′-bicarbazole and/or 9-(6-(9H-carbazol-9-yl)pyridin-3-yl)-9H-3,9′-bicabazole).

The EMLcomprises the second compound DF that is delayed fluorescent material. When holes and electrons meet to form exciton, singlet exciton with a paired spin state and triplet exciton with an unpaired spin state is generated in a ratio of 1:3 in theory. Since the conventional fluorescent materials can utilize only the singlet excitons, they exhibit low luminous efficiency. The phosphorescent materials can utilize the triplet excitons as well as the singlet excitons, while they show too short luminous lifetime to be applicable to commercial devices.

Delayed fluorescent material such as such as a thermally-activated delayed fluorescent (TADF) material, which can solve the problems accompanied by the conventional art fluorescent and/or phosphorescent materials, has been developed. The delayed fluorescent materials DF have very narrow energy bandgap ΔEbetween an excited singlet energy level Sand an excited triplet energy level T(see,). Accordingly, the excitons of singlet energy level Sas well as the excitons of triplet energy level Tin the delayed fluorescent material DF can be transferred to an intermediate energy level state, i.e. ICT state, and then the intermediate stated excitons can be shifted to a ground state (S; S→ICT←T).

Since the delayed fluorescent material DF has the electron acceptor moiety spacing apart from the electron donor moiety within the molecule, it exists as a polarized state having a large dipole moment within the molecule. As the interaction between HOMO and LUMO becomes little in the state where the dipole moment is polarized, the triplet excitons as well as the singlet excitons can be converted to ICT state.

The delayed fluorescent material DF must has an energy level bandgap ΔEequal to or less than about 0.3 eV, for example, from about 0.05 to about 0.3 eV, between the excited singlet energy level Sand the excited triplet energy level Tso that exciton energy in both the excited singlet energy level Sand the excited triplet energy level Tcan be transferred to the ICT state. The material having little energy level bandgap ΔEbetween the singlet energy level Sand the triplet energy level Tcan exhibit common fluorescence with Inter system Crossing (ISC) in which the excitons of singlet energy level Scan be transferred to the excitons of triplet energy level T, as well as delayed fluorescence with Reverser Inter System Crossing (RISC) in which the excitons of triplet energy level Tcan be transferred upwardly to the excitons of singlet energy level S, and then the exciton of singlet energy level Stransferred from the triplet energy level Tcan be transferred to the ground state S. In other words, 25% excitons at the excited singlet energy level Sand 75% excitons at the excited triplet energy level Tof the delayed fluorescent materials DF are converted to ICT state, and then the converted excitons drops to the ground state Swith luminescence. Therefore, the delayed fluorescent material may have 100% internal quantum efficiency in theory.

The second compound as the delayed fluorescent material in the EMLmay be a triazine-based delayed fluorescent material. The triazine-based delayed fluorescent material that can be used as the second compound DF in the EMLmay have the following structure of Chemical Formula 1:

In Chemical Formula 1, each of Rand Ris independently hydrogen or an unsubstituted or substituted C-Calkyl group; and Ris an unsubstituted or substituted C-Cfused hetero aromatic group, an unsubstituted or substituted C-Caromatic amino group or an unsubstituted or substituted C-Chetero aromatic amino group.